Detergent compositions

ABSTRACT

A granular detergent composition containing (a) a granular blend of mixed mono- and di-glycerides of fat-forming fatty acids, said mixture having a melting point of not less than 54*C. with a polyoxyethylene derivative of a higher fatty acid sorbitan ester; and (b) a compound selected from the group consisting of an inorganic water-soluble alkaline detergent salt, an inorganic alkaline sequestering agent, an organic alkaline sequestering agent and mixtures of these compounds. These compositions may contain an oxidizing agent of the oxygen releasing type or the halogen releasing type. These detergent formulations are useful for washing hard surfaces and are especially suitable for dishwashing machines and the like.

Unite States Patent [1 1 Fairs Oct. 2, 1973 DETERGENT COMPOSITIONS [75]Inventor: Robert Roy Fairs, North Umberland, Pnmary "f" W wemblauEngland Att0rneyJulius P. Filcik, Charles R. Wilson and Richard C. Witte[73] Assignee: The Procter & Gamble Company,

Cincinnati, Ohio [57] ABSTRACT Filed! y 3, 1971 A granular detergentcomposition containing (a) a [211 App]- NOJ 139,809 granular blend ofmixed monoand di-glycerides of fatforming fatty acids, said mixturehaving a melting point of not less than 54C. with a polyoxyethylenederivative of a fatty acid so bltan ester; and a com- 252/135, 252/351ound selected from the group consisting of an inorlllltganic watersoluble alkaline detergent alt an inorof Search 95, ganlc alkalinesequestering agent an organic alkaline 252/89, sequestering agent andmixtures of these compounds. These compositions may contain an oxidizingagent of References Cited the oxygen releasing type or the halogenreleasing type. UNITED STATES PATENTS These detergent formulations areuseful for washing 3,549,543 12/1970 Kirstachler 252/135 X hard surfacesand are especially suitable for 3,600,3l7 8/1971 Lintner.... 252/99dishwashing machines and the 3,577,347 5/1971 Monickt. 252/99 2,830,9064 1953 Farback 252 351 x 14 Claims, N0 Drawings 1 DETERGENT COMPOSITIONSBACKGROUND OF THE INVENTION The invention relates to granular detergentcompositions intended primarily for washing hard surfaces, andespecially suitable for use in dishwashing and the like machines. Suchcompositions are hereinafter called dishwashing compositions, andinclude compositions suitable for washing other hard surfaced articles,for example bottles, plastics articles, cutlery, metal goods, dairyequipment etc.

Known compositions of this type normally comprise a major proportion ofalkaline substances such as alkaline inorganic salts,caustic alkalis,sequestering agents and oxidizing and sanitizing agents and the like,together with a minor, but important, proportion of one or more organicwetting agents.

Desirable properties of such dishwashing compositions include:

they should be free-flowing, even after prolonged storage, for easyhandling and dispensing,

they should effectively remove soil, such as food residues, grease etc.,from the surfaces and keep it in suspension during the washing process,

they should generate little or no foam in use, even in the presence offood residues, grease, etc.,

they should have bactericidal properties. In addition they should notcorrode, tarnish or leave perceptible deposits upon the surfaces evenafter repeated washings.

If anionic detergents are used in these compositions in an amountsufficient to have appreciable wetting action, they cause excessive foamin use, the foam interfering with the scouring action of the detergentsolution on the surfaces to be cleaned, and promoting carry over ofsoil-laden detergent solution from the washing cycle to the rinsingcycle of the machine. The lower foaming nonionic detergents aretherefore more often employed, but most nonionic detergents are liquidsor pastes at ordinary temperatures. Hence they tend to make granularcompositions containing them sticky and non-freeflowing. Furthermore,for the same reason, they promote intimate contact between anychlorine-releasing oxidizing and sanitizing agents present in thecomposition, and encourage their decomposition during storage.

BRIEF DESCRIPTION OF THE INVENTION The present invention is based on theobservation that these failings of known anionic and nonionic detergentsand wetting agents can be avoided or reduced, and the desiredcharacteristics of a dishwashing composition can be obtained, by usingcertain emulsifiers which have previously only been considered for usein food preparations, especially in frozen confections such as icecreams.

DETAILED DESCRIPTION OF THE INVENTION According to the invention thereis provided a granu lar detergent composition comprising:

a. from 0.! percent to percent by weight of the composition of anorganic surface-active agent which is a granular blend of 1) mixedmonoand diglycerides of fat-forming fatty acids, said mixtures ofglycerides having a melting point of not less than 54C., with (2) apolyoxyethylene derivative of a higher fatty acid sorbitan ester; and

b. from 80 percent to 99.9 percent by weight of the composition of acompound selected from the group consisting of l. inorganicwater-soluble alkaline detergent salt, 2. an inorganic alkalinesequestering agent,

3. an organic alkaline sequestering agent and 4. mixtures of thesecompounds.

The above compositions are especially effective when in addition theycontain an oxydizing agent. The oxydizing agent may be of the oxygenreleasing type or of the halogen releasing type.

The organic surface active agents suitable for the compositions of theinvention include those described in British patent specification No. 95l ,0] l of Atlas Chemical Industries, Inc; and marketed under the Tradename Tween-mos."

Generally, the preferred organic surface active agents comprise a blendof from 95 to 60 percent by weight of mono and di-glycerides offat-forming fatty acids, said mixture of glycerides having melting pointnot less than 54C, with from 5 to 40 percent of polyoxyethylene sorbitantristearates containing an average of from 8 to 50 moles of ethyleneoxide per mole of sorbitan tristerate. Thus, a preferred organic surfaceactive agent comprises a blend of 60 percent by weight of monoanddi-glycerides of edible fats and oils, containing not less than 22percent, by weight of the blend of monoglycerides, with 40 percent of apolyoxyethylated sorbitan tristearate containing an average of 20 molesof ethylene oxide per mole of sorbitan tristearate. The compositionmarketed as Tween-mos 280VS is particu larly preferred, and is said tohave this constitution. Other suitable agents are Tween-mos 240VS saidto comprise a blend of 80 percent monoand diglycerides of edible fats oroils containing not less than 30 percent by weight of the blend, ofmonoglycerides, with 20 percent of a polyoxyethylated sorbitantristearate containing an average of 20 moles of ethylene oxide per moleof sorbitan tristearate; and a blend of from 97 to percent by weight ofmonoand diglycerides and from 3 to 30 percent by weight ofapolyoxyethylene sorbitan monooleate containing an average of from 8 to50 moles of ethylene oxide per mole of sorbitan monooleate; a preferredagent of this type is Tween-mos I00 VS, said to comprise a blend ofpercent monoand di-glycerides of edible fats or oils containing not lessthan 30 percent by weight of the blend, of monoglycerides, with 20percent of a polyoxyethylated sorbitan monooleate containing an averageof 20 moles of ethylene oxide per mole of sorbitan monooleate.

Normally, the stated organic surface active agent constitutes from aboutl percent to about 10 percent, especially about 2 to about 6 percent, byweight of the dishwashing compositions. Smaller quantities may beeffective for some purposes, for instance down to 0.5 percent or as lowas 0.1 percent. Larger quantities, up to 20 percent or more may beemployed, especially in compositions intended for use at lowconcentrations. In general, the higher percentages of the organicsurface active agent may provide insufficient improved performance tojustify their cost.

It is most surprising that these compounds, previously known only asfood emulsifiers, have now been found to be effective wetting andcleaning agents, and appear to be even more effective than the wellknown nonionic detergents, such as Pluronics (trade name), which arecondensates of polypropylene oxide and polyethylene oxides;polyethoxyalkylphenols; polyethoxy alcohols and the like. They have thefurther advantages of being themselves granular solids at ordinaryatmospheric temperatures (melting at 57C or higher), so that they do notcause stickiness in granular compositions in which they areincorporated. For the same reason, they do not promote intimate contactbetween oxygen or chlorine releasing agents and the other components ofdishwashing compositions containing them. As a result of their limitedsolubility in water and their high melting point, they are particularlysuitable for use in washing processes at relatively high temperaturesuch as are commonly met in dishwashing and like machines, for instanceat about 55C to boiling, preferably about 57C to 75C. They may also beused in manual dishwashing provided that temperatures over at leastabout 50C can be employed. In these conditions, the compositions of theinvention generate little or no foam.

Apart from the small but essential proportion of organic surface activeagent, the compositions of the invention comprise inorganic watersoluble alkaline detergent salts, especially alkali metal, for example,sodium or potassium (especially sodium) carbonates and silicates;inorganic alkaline sequestering agents such as phosphates andpolyphosphates, or borates; organic alkaline sequestering agents such asaminopolycarboxylates, for example, sodium nitrilo-triacetates or sodiumethylenediamine tetra acetates, and polyhydroxycarboxylates may bepresent. Other organic sequestering agents found to be useful in thisinvention include mellitates, benzene penta carboxylates, citrates,gluconates, oxydiacctates, oxydisuccinates and mixtures thereof.

The preferred inorganic components are penta sodium tripolyphosphate,tetra sodium pyrophosphate and sodium meta silicate.

Suitable oxidizing and sanitizing agents include peroxy salts such assodium perborate, percarbonate, peroxy monosulphate and the like, andagents generating hypochlorite or hypobromite ions in solution such aschlorinated tri-sodium or other phosphates, and N- chloroorN-bromo-organic compounds such as sodium dichloroisocyanurate,trichloroisocyanuric acid, N-chloroand N-bromo-toluene or -benzenesulphonamide, and the like. These substances serve both to destroybacteria and to oxidize certain components of the soil so that it ismore readily removed in the washing process, and to minimize spotting ofdishes etc., after drying, for example in heat, without wiping.Generally, preferred compositions contain a chlorine releasing agent,especially chlorinated trisodium phosphate or a chlorinated isocyanuricacid or a salt thereof.

The proportions of these compounds can be varied within wide limitsaccording to the required properties of the composition. Thus veryeffective compositions contain from about 10 to 80 percent, especially20 to 50 percent, sodium tripolyphosphate, anhydrous, preferably ingranular form (for example such that not more than 20 percent passes a100 mesh BSS sieve); from 5-60 percent sodium silicate, preferablyanhydrous sodium meta silicate, but any solid, optionally hydrated,sodium silicate having weight ratio SiO,:NA O in the range [:1 to 3.4:1may be used; from to about 30 percent of anhydrous sodium carbonate,preferably in dense granular form; a source of hypochlorite ion, inamount providing from about 1 to percent of available chlorine, such assodium dichloroisocyanurate, trichlorocyanuric acid, or chlorinatedtrisodium phosphate. From 0 to percent of an oxidizing agent such as thealkali perborates, percarbonates and perox- 5 ymonosulphates may beused. Generally the amount of sodium silicate, especially sodium metasilicate, should not exceed about 70 percent and that of sodiumcarbonate should not exceed about 30 percent, since higher levels maycause some attack on glass or glazed surfaces. This composition shouldpreferably contain insufficient moisture completely to hydrate thehydratable salts present. The remainder comprising from O to 30 percentanhydrous sodium sulfate.

The term available chlorine as used above and hereinafter presents thelevel of molecular chlorine (C1 having equal bleaching power. Since oneatom of active chlorine in compounds providing hypochlorite ions insolution has the same activity as one molecule (i.e., two atoms) ofmolecular chlorine, the percentage of available chlorine stated, byweight, is double the weight percentage of reactive chlorine. Thus forexample pure sodium hypochlorite, having the formula NaOCl would contain47.7 percent reactive chlorine by weight, expressed as 95.4 percentavailable chlorine.

Neutral fillers, such as sodium chloride, sodium sulphate etc. may bepresent, for instance, from 0 to about 30 percent of sodium sulphate(calculated as anhydrous salt). Various other components may be includedfor various purposes, such as perfume, colouring matters, tarnishinhibitors such as benzotriazole, iron chelating agents, such as sodiumgluconate, which prevent development of stains on aluminum and ahaze-like deposit on glazed surfaces after repeated washing. Though notusually necessary or desirable other organic wetting agents and othersanitizing agents may be included in special cases.

The above mentioned inorganic salts may be at least partially hydratedwhen incorporated in the composition, provided that the free flowingproperties of the composition are not impaired. Thus there shouldnormally be sufficient hydrate-forming capacity available to absorb anymoisture added during preparation of a product, (as explained below) andto enable the product to remain free flowing despite normal changes ofhumidity of the atmosphere to which it is exposed.

The compositions may be prepared by any effective method. Convenientlythe dry particulate components, for example, salts, Tween-mos compounds,but excluding the oxidizing or chlorine-releasing agent, may be mixedtogether in any suitable apparatus, such as a rotating drum or cubemixer, inclined pan mixer etc. Liquid components such as perfume and/oran aqueous dispersion of colouring matter are admixed, most convenientlyby spraying them on the particular mixture. Any water present or addedis absorbed by incompletely hydrated salts in the composition. Finallythe oxidizing or chlorine-releasing agent is added as a particulatesolid.

The following Examples illustrate the invention:

EXAMPLE I The following compositions were prepared by dry mixing thefirst four components listed, spraying on thoseso indicated, and finallydry mixing the chlorinated trisodium phosphate.

A percent Composition by by weight weight Anhydrous granular sodiumtripolyphosphate 45.2 45.5 Anhydrous sodium metasilicate (beads) 11.0011.00 Sodium Silicate "M (Crystalline hydrate,

SiO,: Na,O:3.3:l by weight). 11.00 11.00 Tween-mos 280VS 2 Pluronic L622 Perfume sprayed on 0.1 0.1 Dyestuff do. 0002 0.002 Water do. 07 0.4Chlorinated trisodium phosphate (containing about 3% available chlorineby weight) 30 30 Composition A was according to the invention and was afree flowing dry powder. The reference composition B was a slightlysticky powder, tending to form soft lumps on standing. Their cleaningefficiency was determined by using them in a Kenwood Model A 1212Dishwashing machine, using its operating cycle 11, at a concentration of0.75 percent by weight in water 12H (172 ppm hardness as CaCO In themachine, water temperature was 57-60C. To provide a representative loadfor the machine 44 dinner plates, used in a Canteen for a main luncheoncourse, i.e., meat, fish etc., were obtained and half were washed witheach detergent composition. After washing in the machine the number ofsoil marks remaining was counted. The plates were then carefully handwashed, and dried, for re-use. This was repeated for a total of fivewashes. In every wash the number of marks on plates washed by thecomposition A of the invention was less than that on plates washed bythe reference composition B, and overall the average values were:Product of the invention 1.1 marks per plate, Reference product 1.8marks per plate.

EXAMPLE 11 Similar washing performance was provided by the followingcompositions, which also were dry free flowing powders. They containedadditives which reduced the tendancy of the inorganic components totarnish cutlery and they reduced the staining of aluminum in thepresence of iron-bearing water or soil. The quantities are percentagesby weight.

Products C and D are intended for use at about 1% concentration in thewash liquor; product E, for use at about 0.5% concentration.

EXAM PLE 111 Compositions of the following formula were prepared andtheir cleaning performance tested as in Example l, except that testswere replicated two or three times as indicated below:

X: by weight 40.4

Sodium tripolyphosphate Sodium metasilicate 13.5 Sodium silicate(SiO,:Na,O by

weight 3.311) 13.5 Chlorinated trisodiumphosphate 30.1

Color/water/perfume Organic detergent Our EXAMPLE 1 Granularcompositions of the formula given in Example 111, containing Tween-mos280 VS as organic detergent, and for comparison Pluronic L 62 (Tradename) were prepared. The products were packed in cardboard sidedlever-lid canisters and stored in (1) a constant temperature roommaintained at 26.5C., and (2) in a warehouse whose temperature variedwithout special control from about 265C. to about 0C. The percentagelosses by weight of available chlorine after the stated times were:

265C. Warehouse Room Tween-mos product 4 months 31% 6 months 46% 7Pluronic product 4 months 63% 6 months 78% 34 Having fully described theinvention, what is claimed l. A granular detergent compositioncomprising:

a. from 0.1% to 20% by weight of the composition of an organicsurface-active agent which is a granular blend of (1) mixed monoanddiglycerides of fatforming fatty acid, said mixtures of glycerideshaving a melting point of not less than 54C., with (2) a polyoxyethylenederivative of a higher fatty acid sorbitan ester which contains anaverage of from 8 to 50 moles of ethylene oxide per mole of sorbitanester; and

b. from 80 percent to 99.9 percent by weight of the composition of acompound selected from the group consisting of 1) inorganicwater-soluble alkaline detergent salt, (2) an inorganic alkaline sequestering agent, (3) an organic alkaline sequestering agent and (4)mixtures of these compounds.

2. The composition of claim 1, wherein component (a) is a blend of fromto 60 percent by weight of said glycerides and from 5 to 40 percent byweight ofa polyoxyethylene sorbitan tristearate containing an average offrom 8 to 50 moles of ethylene oxide per mole of sorbitan tristearate.

3. The composition of claim 1, wherein component (a) is a blend of from97 to 70 percent by weight of said glycerides and from 3 to 30 percentby weight ofa polyoxyethylene sorbitan monooleate containing an averageof from 8 to 50 moles of ethylene oxide per mole of sorbitan monooleate.

4. The composition of claim 2, wherein component (a) is a blend of 60percent by weight of monoand diglycerides of edible fats and oils,containing not less than 22 percent by weight of the blend, ofmonoglycerides, with 40 percent of a poly-oxyethylated sorbitantristearate containing an average of 20 moles of ethylene oxide per moleof sorbitan tristearate.

5. The composition of claim 2, wherein component (a) is a blend of 80percent by weight of monoand diglycerides of edible fats and oils,containing not less than 30 percent by weight of the blend ofmonoglycerides, with 20 percent of polyoxyethylated sorbitan tristearatecontaining an average of 20 moles ethylene oxide per mole of sorbitantristearate.

6. The composition of claim 3, wherein component (a) is a blend of 80percent by weight of mono and diglycerides of edible fats and oils,containing not less than 30 percent by weight of the blend, ofmonoglycerides, with 20 percent of a polyoxyethylated sorbitanmonooleate containing an average of 20 moles of ethylene oxide per moleof sorbitan monooleate.

7. The composition of claim 1 which also includes an amount of chlorinereleasing agent sufficient to provide from 1 percent to 5 percentavailable chlorine.

8. The composition of claim 7 wherein the chlorinereleasing agent is achlorinated isocyanuric acid or salt thereof.

9. A composition as claimed in claim 7 wherein the chlorine-releasingagent is chlorinated trisodium phosphate.

10. The composition of claim I which also includes from 0 percent to 20percent by weight of the composition an oxidizing agent selected fromthe group consisting of perborates, percarbonates and peroxymonosulphates.

11. The composition of claim 1 wherein component (b) (3) is selectedfrom the group consisting of water soluble citrates, mellitates, benzenepenta carboxylates, oxydiacetates, oxydisuccinates, gluconates, andmixtures thereof.

12. The composition of claim 1 wherein component (b) is from 10 topercent of anhydrous sodium tripolyphosphate, from 5 to 60 percent ofsodium silicate having a weight ratio SiO to Na O in the range of from1:1 to 3.4:1, a source of hypochlorite ion in an amount providing from 1to 5 percent of available chlorine, from 0 to 30 percent of anhydroussodium carbonate and from 0 to 30 percent anhydrous sodium sulfate.

13. The composition of claim 1 wherein there is present from 1 percentto 10 percent by weight of component (a).

14. The composition of claim 1 wherein there is present from 2 percentto 6 percent of component (a).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,763,047 October2, 1973 Patent No. Dated Inventor) Robert Roy Fairs It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Columfi ine :54 "compounds" should ead "components-- Column 4, linehlS"presents should read -rep resents Column 5, line53 (isooyanurate shouldread -isocyanurate Column 6, line 32 "78% under Warehouse column" shouldread -78% under. Room" column 1 Column 7, line l8, fdhlorine" shouldread -a chlorine-- Signed and sealed this 27th day of August 1974 (SEAL)Attest:

' MCCOY M. GIBSONQCQIR. a c. MARSHALL DANN Attesting OfficerCommissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION 3 ,763,047 7 Dated October 2, 1973.

Patent No.

Inventor) Robert Roy Fairs It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 3 line "54 "compounds" should read -'-components- Column 4 line"15 "presents" should read -rep resents-- Column 5 line 53 (isocyanurateshould read --isocyanurate-- Column 6 line" 32 "78% underWarehousecolumn"- should read --78% under Room' columrv- Column 7 linel8 "chlorine" should read -a tzhlorine-Q Signed and sealed this 27th dayof August 1974 (SEAL) Attest:

McCOY M. srBsoNfJR. n r c. MARSHALL DANN Attesting Offier r ICommissioner of Patents

2. The composition of claim 1, wherein component (a) is a blend of from95 to 60 percent by weight of said glycerides and from 5 to 40 percentby weight of a polyoxyethylene sorbitan tristearate containing anaverage of from 8 to 50 moles of ethylene oxide per mole of sorbitantristearate.
 3. The composition of claim 1, wherein component (a) is ablend of from 97 to 70 percent by weight of said glycerides and from 3to 30 percent by weight of a polyoxyethylene sorbitan monooleatecontaining an average of from 8 to 50 moles of ethylene oxide per moleof sorbitan monooleate.
 4. The composition of claim 2, wherein component(a) is a blend of 60 percent by weight of mono- and di-glycerides ofedible fats and oils, containing not less than 22 percent by weight ofthe blend, of mono-glycerides, with 40 percent of a poly-oxyethylatedsorbitan tristearate containing an average of 20 moles of ethylene oxideper mole of sorbitan tristearate.
 5. The composition of claim 2, whereincomponent (a) is a blend of 80 percent by weight of mono- anddi-glycerides of edible fats and oils, containing not less than 30percent by weight of the blend of mono-glycerides, with 20 percent ofpolyoxyethylated sorbitan tristearate containing an average of 20 molesethylene oxide per mole of sorbitan tristearate.
 6. The composition ofclaim 3, wherein component (a) is a blend of 80 percent by weight ofmono- and di-glycerides of edible fats and oils, containing not lessthan 30 percent by weight of the blend, of mono-glycerides, with 20percent of a polyoxyethylated sorbitan monooleate containing an averageof 20 moles of ethylene oxide per mole of sorbitan monooleate.
 7. Thecomposition of claim 1 which also includes an amount of chlorinereleasing agent sufficient to provide from 1 percent to 5 percentavailable chlorine.
 8. The composition of claim 7 wherein thechlorine-releasing agent is a chlorinated isocyanuric acid or saltthereof.
 9. A composition as claimed in claim 7 wherein thechlorine-releasing agent is chlorinated trisodium phosphate.
 10. Thecomposition of claim 1 which also includes from 0 percent to 20 percentby weight of the composition an oxidizing agent selected from the groupconsisting of perborates, percarbonates and peroxy monosulphates. 11.The composition of claim 1 wherein component (b) (3) is selected fromthe group consisting of water soluble citrates, mellitates, benzenepenta carboxylates, oxydiacetates, oxydisuccinates, gluconates, andmixtures thereof.
 12. The composition of claim 1 wherein component (b)is from 10 to 80 percent of anhydrous sodium tripolyphosphate, from 5 to60 percent of sodium silicate having a weight Ratio SiO2 to Na2O in therange of from 1:1 to 3.4:1, a source of hypochlorite ion in an amountproviding from 1 to 5 percent of available chlorine, from 0 to 30percent of anhydrous sodium carbonate and from 0 to 30 percent anhydroussodium sulfate.
 13. The composition of claim 1 wherein there is presentfrom 1 percent to 10 percent by weight of component (a).
 14. Thecomposition of claim 1 wherein there is present from 2 percent to 6percent of component (a).